DE2429729C3 - Image recording material - Google Patents

Description

The invention relates to an image recording material for electrical registration or image recording with at least one electrically conductive compound, an image-forming agent and a Binder-containing recording layer on a support. The recording material of the invention is suitable for registering or recording different received signals, such as signals of facsimile machines, outputs of computers and their output devices, data of various kinds of Measuring devices for industry, medicine, trade and commerce and various purposes,

The recording or registration of electrical telephones Signals as an image decreases with the development of image radio and other telecommunication devices from year to year to. The most extensively used to date for such recording purposes are for example electrical discharge recording, electrolytic recording etc.

In electrical discharge recording, an image is created by either taking a white pigment layer on an electrically conductive black layer or an electrically conductive thin Metal layer of, for example, aluminum on the above-mentioned electrically conductive black Layer and then the surface layer of white pigment or the thin metal layer through electrical discharge by means of a stylus (hereinafter referred to as “pen”) with removal the surface layer and exposure of the black layer underneath.

In electrolytic recording, an image is created by first placing a sheet of paper with a impregnated electrolytic solution and so brought into a moist state and through this one electric current is sent by means of the pen. The resulting image is either through a colored substance formed by the reaction between the "ionized" substance coming from the pen Metal and the electrolyte is created or by a colored decomposition product that is produced by electrolysis of the electrolyte present in the paper is formed by the electrical current supplied via the pen will.

In the recording method by electrical discharge arise as the surface layer through Heat of the electrical discharge generated by the pen is perforated, inevitably some inconvenience like a very strong * irritating or annoying odor, atomizing particles from the Perforation of the surface layer, considerable pen wear, and other disadvantages. In addition, there is a likelihood that mechanical effects such as creasing or creasing, Pressures, etc., to which the coatings are subjected, expose the black layer so that the Paper is easily "colored" or is defective. In addition, the un'.er of the surface layer that is used for Promotion of the discharge effect is made thin, (underneath) the black layer not perfect covered so that the basic color of the Aulfzeichbiw. Recording paper tends to be gray rather than white, which diminishes its appearance.

On the other hand, the recording paper or recording material is in the electrolytic recording process of the wet type of poor storability and the quality of the on it generated image is affected by the electrolyte bleeding. In addition, the paper suffers from deformation like "wrinkling" on its surface as a result of drying out after the picture was taken. These deficiencies are extremely troublesome in such a wet type recording method.

In] A patent publications 22341/1963 and 29630/1969 will describe an electrosensitive recording material of the dry type in which

an image is obtained by electrically dispersing one in an insulating resin layer free metals reducible metal compound is reduced by current flow to the free metal. With this one Electrosensitive recording material are, however most metal compounds of relatively high electrical conductivity colored while less Colored metal compounds have a low electrical conductivity and therefore chemical and require physical treatments for the ι ο electrical current to flow through. Such treatments however, they cause coloring of the metal connections and consequently an increase in depth the base color of the recording material to a considerable extent. It also leads to difficulties in the electrical conduction through the insulating resin dispersion to the occurrence of undesirable bad smell infoige of the heating by electrical discharge during the recording resp. Registration and - among other flaws - the pen wears out considerably.

Furthermore, in the JA patent publications 5476/1967 and 13239/1967 described a method in which a an electrically conductive thin layer on a white or transparent substance such as silica, etc. Deposition from the vapor phase is formed after which the substance in the base material for electrical conduction is dispersed. This way of working is complicated and technically difficult to carry out.

Finally, in the older DE-OS 24 14 201 an electrosensitive recording material is proposed been, which as an electrically conductive material containing at least one zeolitic water Connection contains.

This image recording material is indeed for electrical} S see registration of images useful, but only in a limited manner, which are used there as an electrically conductive material by the very specific substances.

The object of the invention is to provide an image recording material for electrical registration or image recording to make available, which works trouble-free, is easy to handle and images of high Quality.

The solution to this problem is according to the invention that the image recording material as electrically conductive "; connection at least one porous Compound with polar substance contained therein - with the exception of containing zeolitic water Compounds, contains.

As will be understood from the description below, in the image recording material of the invention a large number of porous compounds into consideration, so that the image recording material without technical difficulties and can be produced very variably.

The image recording material of the invention is excellent in electrical conductivity and thus has an improved recording quality. With the recording material according to the invention, independent of the humidity of the surrounding atmosphere, stable images can be obtained under practically dry conditions. Because of the high electrical Leitfähigkeil the image recording material already responded to l <: I e changes in the acting ^h 5 amount of electricity, so that images can be recorded of high quality and excellent reproduction of the picture "is achieved with good sound.

Finally, the image recording meterial can Invention can be produced by a very simple procedure, and it also has a high Storage stability over long periods of storage. In addition, the image recording material is of the invention are non-toxic and therefore safe to use.

With the image recording material of the invention, desired images become known per se Way recorded or registered by an electric current in the active recording layer is sent.

The invention is explained in more detail below with reference to the drawings.

F i g. I to 3 are different diagrams showing the structure of the image recording Materials and the recording method working with it in different types illustrate.

The image recording material according to FIG. consists of a base layer 3 made of any suitable material, an electrically conductive ... intermediate layer 2, which are arranged on the base layer and a surface layer 1 for recording on the Intermediate layer. This planar or web material for image recording is used to thereafter to obtain images by the electric discharge recording method according to the invention.

The upper or writing layer 1 consists of a porous compound (A) containing a polar substance therein, an image-forming agent (B) and a binder for binding these two substances.

The image recording material according to FIG. 2 consists of the base layer 3, the electrically conductive intermediate layer 2 on the base layer 3 and a further electrically conductive layer 5 which corresponds to the upper writing layer 1 of FIG. 1 corresponds to as described above, only that here the image-forming agent (B) is excluded; this layer 5 is arranged on the intermediate layer 2 and on top of the layer 5 there is arranged an image-forming layer 6 which contains the image-forming agent (B) therein. In this case, the so-called writing layer, as it is in the previous embodiment according to FIG. 1 is used, referred to as a combination of electrically conductive layer 5 and vapor-generating layer 6.

Finally, there is the image recording material as shown in FIG. 3 only from the base layer 3 and the Writing layer 1, which is the same as that of the image recording material according to FIG. 1.

With all these types of carrion according to FIG. 1 to 3 reference numeral 4 denotes an electricity source, 7 denotes a pen, and 8 is one Return electrode :. The electrode 8 can directly from the electrically conductive layer 2 or the writing layer 1 or the image-forming layer 6 be taken. The polarity of the electricity impressed on the pen 7 can be either positive (+) or negative (-), or alternating current can be used.

The porous substance (hereinafter referred to simply as compound A ) to be used as an electrically conductive agent or agent in the context of the invention, which contains a polar substance, is to be understood as having the following physical properties, namely:

I) The compound α has »pores« or »cavities

me «within their molecular structure, in which a loosely bound polar substance (which will be described in more detail later) can be held. Even in this state that a sufficient amount of polar substance is contained in these pores or voids. Compound A shows no "stickiness", as can be seen in the hygroscopic and blooming phenomena which generally occur with sodium chloride and similar salts. but maintains an apparently dry state.

2) Compound A does not lose its crystal structure even if the polar substance contained therein is completely removed under the action of heat, reduced pressure or any other means.

j) Compound A shows good electrical conductivity in view of the polar substance and different types of ions with which it can coexist

4) The compound A can develop its electrical conductivity by adsorbing enough water even if it is left in the natural atmosphere.

As mentioned in the previous paragraphs. J ¹ C compound .4 has very special physical properties. The inventors have recognized these physical properties of the compound A and, after extensive and careful investigations; and experiments, found that the image recording material produced by a master in which the compound A is dispersed in a binder has the properties of the compound in can have practically the same degree as the connection A pe ^ se int

Connections Λ. which are rinwerdha 'for the purposes of the invention are as follows:

L ion exchange resin

S ^ r'heüsche. Hirze. which are mainly made of porous r i. ^ [- polymers containing ion exchangers.-.- en Saij-egroup. or base groups exist. fall under this category. Types of such ion exchange resins are cationic, anionic and ampho- • eric ion exchange resins.

The composition of the high polymers forming the main component of the ion exchange resin can be any of the Pohs'.yrol-amine type. Phenol-me-'hviensu if on acid type. Polystyrene sulfonic acid type. Phcnol- ■ ormaidehvd-polyamine type. Methacrylic acid type and vinyl resins.

The acid groups can be, for example, sulfonic acid groups. f-SC / JH). Carboxyl groups (-COOH) and phenolic hydroxyl groups (-OH). The basic groups can, for. B. amino groups (- NH?), Substituted amino groups (-NHR. -NRR ') and quaternary ammonium salt groups (-N-RR'R-).

2. Electron exchange resin

High polymer compounds that exhibit electron exchange fall under this category for which Polyvinyl hydroquinone. Hydroquinone formaldehyde resin. Dioxyphenyl alanine polymers, etc. may be examples.

3. Hydrophilic crosslinked copolymers

which consist of "ternary" components A, B and C, component A being formed by 60 to 90% by weight of a heterocyclic N-vinyl monomer represented by N-vinyllactam, component B by 40 to 10% by weight of one of vinyl acetate and methyl methacrylate selected monomers and component C is formed, for example, by < polyethylene glycol dimethacrylate , of which 0.5 to 12% by weight to the total amount of the components A and N are added.

4. Porous polyester resin

κ. The polyester resins are represented by those generated by the following procedural step:

a) A means is provided for the formation of an internal phase, which is provided by water or an im a liquid consisting essentially of water is formed;

b) A means is provided for the formation of an external phase, which is formed by a polymerizable organic liquid, which consists of the following two elements:

Component a: is a polyester made from polycarboxylic acid and polyhydric alcohol, whose Molecules have at least one functional group through

^ -CO-CH = CH-CO-

is given, and

component b: is a low molecular weight pol ;, -.ierizable liquid monomeric compound. which can be copolymerized with component a and is capable of containing therein a low molecular weight, polymerizable non-liquid monomeric compound / u contain:

c) Production of an oil-water emulsion with water ·. <As an emulsifying agent in the presence of a

or two or more kinds of inorganic metal compounds having poor solubility in Water such as B. sulphides, hydroxides and oxides of mercury, lead bismuth. Copper. Cadmium. j. Antimony. Nickel, cobalt, iron. Zinc. Manganese.

Aluminum and chrome: and

d) bulk polymerization of this oil-water emulsion in the presence of a polymerization catalyst and depending on the need for a polymerization accelerator

4λ gers to create a porous synthetic

Resin, with some or all of the internal phase forming agent being produced synthetic resin is removed as necessary.

5. A substance with micropores contained therein

This substance is created by ma. A uniformly mixed solution of - mainly - a condensed copolymer resin of

s? Dichlorodiphenylsulfon Bisphenol (hereinafter referred to simply as "Polysulfone"), chloroform as the solvent and an alcohol with 1 to 5 carbon atoms as a non-solvent in a flat layer and then at a temperature below the

Ίο softening point of the resin with formation of Micropores in the resin layer are subjected to evaporation and drying.

6. Silicas and Silicates a) Porous silicas of the formula

known as silica gel or silica airgel;

b) Silicates of the formula

λ Μ, O · VSi

which occur naturally as "sticky"minerals; Examples are amorphous silicates such as allophane, hisingerite, etc., and crystalline phyllosilicates (with leaf structure) e.g. B. the montmorillonite group, pyrophyllite group, talc group, Gi.mmergruppe, koalin group, chlorite group. Vermiculite etc.

Porous silica glass that is available as an intermediate product in quartz glass production.

7. aluminum silica,

Different types of condensed acids can be specified here, for the more natural ones Zeolite is typical. This is also known as aluminum silicate and by the following general formula reproduced:

Molecular sieve A *) Nai .- (Ali.'SiWi) M) NaAIO. '

29 HK)

Molecular sieve X *) Na ^ AL-Si ^ O »*) ■ χ H ₂ O (X = O) Molecular sieve Y ') NaX) ■ ΛΙ2Ο1 J -6SiO.' ■ vf molecular sieve SK *) practically identical to Faujiisi liemerkut: *) synthetic zeolite.

(3) Chabazite group:

Chabazite R *) (Approx ■ Na2) AL'SM Mg ■ Na: same as Oi2 · 6 H2O Gmelinite S ^# ) (Na2Ca) Ab.SUOi H ₂ O same as 2 6 H2O Erionite T *) (Approx Ca (AIzSUOi2) 6 same as • K ₂ ) ■ AI ₂ Si) C ■ b the Lcvynite the IhO Molecular sieve the Chabazil Molecular sieve Gmelinite Molecular sieve Elionil

Note: *) synthetic zeolite.

ΛΙ..Ο / ;; SiO: ■

with (3SmS 10). where: M '· and M · /. are divalent and monovalent metals, most of which are usually denoted by Ca-' · and sometimes Sr- ¹ ·. Ba- '' and K ■ are formed, all of which can be replaced by other cations. These zeolites have specific "cavities" or "pores" in the three-dimensional skeletal structure in which the replaceable ions mentioned above are held together with water molecules. In addition to water, organic solvents can be absorbed in the voids, and solvents of high polarity can be selectively absorbed. Insofar as the zeolite water originally present in the cavities of these zeolites is concerned, such compounds as constituents of the image recording material are outside the scope of the invention. There is a great variety of synthetic zeolites which have practically the same three-dimensional skeletal structure as the natural zeolite and which are of this in terms of fundamental. Properties are not much different.

There are also natural and synthetic compounds which have completely different chemical compositions from zeolite, although they are the same Have basic properties, d. H. Have cavities and their structures during absorption and desorption of water does not change. Such compounds are called zeolite-like compounds, which are also used for the Purposes of the invention are useful.

Both natural and synthetic zeolites used in the present invention can be classified as follows:

(1) Analcime group:

Analcite NaAISi2OeH2O

Pollucite (Cs, Na) AlSi2Oe χ HzO (x <10)

Viseit CaioNa2AhoSi6Pio (H3) i2 (H20) i6

Ο96

Kehoesit

(4) Natrolith group:

Natrolite
- <Mcsolit

Scolecite

Thomsonite

Edingtonite
\ o Gonnardit

Rhodesite

Mountainit

NaZ (AIzSilOm) 2 H2O Na2Ca: (AlbSitO) o) ■ 8 Η.Ό Ca (ALSi] OiO) ■ 3 H2O NaCa2 (AhSi502o) · 6 HzO Ba (AbSi] OtO) ■ 4 H2O Na2CA (AUSieO20) 6 H2O KNaCa2 (H2SieOzo) 5 H2O KNazCa2 (HSi8O20) ■ 5 H2O

(5) Harmatom group:

- ¹⁵ Harmatom Ba2 (AUSii2O3. ') ■ 4 H2O

Phillipsite (K.Nai-, JsAhSinOiz 10 Η.Ό

Gismondite Ca (AbSbOs) 4 H2O

Molecular sieve B *) Naz (AbSi3Oin) 5 H2U

Garronite NaCa ₂ 5 (AbSi5Oih): 13.5 H2O

Bermerkiing: *) synthetic zeolite.

(6) Mordenite group:

Mordenite NafAISisOtz) 3 HzO

D'achiardite (Na2Ca) 2AUSizo048 · 12 HzO

Ferrierite Nai.5Mg2 <Al5.5Si30.5O72) ■ I8H2I

Zeolone the same as mordenite

so (7) zeolites
Heulandit
Cliroptilotite

indefinite structure:

Ca (AbSi7Oi8) 6 H2O

Stilbit

(2) Sodalite group:

Hydrosodalite Faujasite

5H2O

Ca (AbSi7Oie) 7 H2O Ca (AbSi6Oi6) ■ 5 H2O (Sr ₁ Ba ₁ Ca) AbSieOi 6 - 5 H2O Ca (AlSbOe) · 4 H2O Ca (AbSisOi4) - 3 H2O (K, Ca, Na) i2c [(A !, Si) 58oOi ieo] 690 H2O

[KNa (Ca, Mg, Mn)] i2o- (AI160S1200O; ») 320 H2O H2O

H2O

Epistilbit Brewsterite Laumontite Yugawaralit Paulingite

Ashcroftin

Bikitait

The above compounds are also useful for the present invention.

809

The protruding :! listed compounds are all Applicable for Lrfindiing. In particular, will be however, preferred compounds that have a large cavity volume or high porosity and a have a high content of polar compounds and therefore show good electrical conductivities.

/.eolite-like compounds 8. Basic aluminum-magnesium carbonate c

These compounds are represented by the following general formula:

Mg ₁ AI ₁ (OI I) ,,. ".... {CO, ), -! I IU)

where: v. y and / are integers that represent the relationships

suffice and a is equal to zero or an integer that corresponds to the relationship

0 <

χ 4 y

enough.

The polar substance identified in the above detailed compound A as the useful active Component can be included for the purposes of the invention can be demonstrated by the following examples:

Polar solvents such as:

Water - except for zeolitic water originally present -, alcohols, ammonia, dimethylformaldehyde; and inorganic salts such as sodium, _s hydroxide, potassium hydroxide, lithium chloride, magnesium chloride, sodium chloride, calcium chloride, sodium iodide, potassium iodide, sodium bromide, potassium bromide. Furthermore, other various electrolytes can be used. Of these, the following are to be listed: Carboxylic acid salts of compounds of the formula RJO (CH ₂ ) ,,], · COOHB

ROCO (CH ₂ J _n ■ COOH-B

(where B is an organic amine), sulfuric acid derivatives such as: triethanolamine salt of cetylsulfonic acid, diethanolamine salt of alkylsulfonic acid, naphthalene sulfonate, sodium salt of oleylbenzimidazole sulfonic acid, etc., phosphoric acid derivatives such as. B. various types of salts of phosphonic acid, phosphinic acid, phosphite esters, phosphoric acid esters, etc., alkylamine salts such. B. l-octadecyl-S-methyl-biguanide hydrochloride, dibutylphosphoric acid-tetraethylene pentamine salt , etc. salts of cyclic amines such. B. heptadecylimidazoline, dimethyl-amino-acetoguanamine, etc. salts of amidamines of higher fatty acids and lower polyamines such. B. N-monoacetyl-ethylenediamine, etc., salts of ester amines such. B. the ester amine of stearic acid and triethanolamine or the stearic acid ester of ω, ω'-diaminopropyl-octadecyl-ethylene glycol ether, etc., quaternary ammonium salts such. B. Alkyldimethylbenzylammoniumsalz, / Ikyltrimethylammoniumsalz etc. · and salts such as. B. guanidine salt, alkylalanine, alkylaminosulfonic acid, etc., which are obtained by reacting maleic anhydride with alkylamine.

For the impregnation of the porous compound A with the polar substance, different auxiliaries such as heating, application of reduced pressure, etc. can be used depending on the situation. However, effective impregnation can be achieved by simply leaving the porous compound A and the polar substance under the natural conditions in case the latter is water. Also, when the required level of electrical conduction for image recording cannot be achieved by impregnation with water alone as a polar substance, any of the foregoing organic or inorganic electrolytes can be used in conjunction therewith for more effective results in terms of image recording. According to the invention, the Imprägmenmgsverliältnis the polar substance in the porous compound A is usually from about 10 to 7 ¹⁾ wt ° / o or more particularly approximately 30 to 70 wt .-%.

The imaging agents as used here are those which are suitable for imaging are capable of changing energy through the application of electricity. It can be any known one Compound are used such as color formers of the oxidation type, color formers from Reduction type, pH indicators, heat-sensitive color formers and the like.

As color formers of the oxidation type, leuco compounds of diphenylmethane colors such as Michler's Meth.in bases like

Bis (p-dimethylaminophenyl) methane,
di

(9-ethyl-6-methyl-3-carbazolyl) -p-dimethyl-

aminophenyl methane etc. and

Leukoauramine like

Leucoauramine, Ν, Ν-diethyl-leukoauramine,

Phenylsulfonamid-bis- (p-dimethylaminophenyl) -

methane,

Bis (p-dimethylaminophenyl) benzotriazyl

methane,

Bis (p-diethylaminophenyl) morphonylmethane

etc.;

Leuco compounds of

Triphenyl methane colors like

Diaminotriphenylmethane like

Leuco malachite green.

3,3'DicarbazoyIphenylmethane etc.,

Triaminophenyl methanes such as

Leuco crystal violet,

9.9'9 "triethy! -3.3'3" -tricarbazoly! Methane

etc. and

Hydroxy-triphenylmethane such as

ßis- (3-methyl-4-hydroxy-5-carboxyphenyl) -

2,6-dichlorophenyl methane,

Bis (3-methyl-4-hydroxy-5-carboxyphenyl) -

4-diethyl aminophenyl methane, etc .;

Leuco compounds of xanthene such as

3,6-di (dimethylamino) xanthene;

Leuco compounds of acridine paint such as

ypy

3,6-di- (dimethylamino) -acridine, etc .; Leuco compounds of azine dyes such as 2-methyl-3-amino-7-dimethyl-amino-5,10-dihydrophenazine, 3,7-diamino-5-phenyl-5,10-dihydrophenazine etc.;

Leuco compounds of oxazine dyes such as 3,7-di (dimethylamino) phenoxazine, etc .; as well as leuco compounds of thiazines such as 3,7-di (dimethylamino) phenothiazine and the like.

to be named.

Furthermore, Rcdiikiionskös can by from indigo and Irdigoid colors. I.cuko-ferrocyanin and l.eukobasc-Küpcnfarbstofi: of para-quinones such as benzoquinone dyes, Naphlhocliinon dyes, anthraquinones, etc .; aromatic amino compounds such as p-amino-cliphenylamine, Diphenylbenzidine. Oxidation base substances, the oxidation colors form such as phenols such as 4-methoxy-inaphthol, 1,5-dihydroxynaphthalene, etc .; and reducing bodies of sulfide colors such as 2-Mercap: o-3-hydroxy-7-dimethylaminophenothiazine etc. are listed.

Tetrazo lium salts such as phenyltetrazolium chloride. Ditctrazolium chloride etc.; ionic salts of long-chain aliphatic acids such as ferric stearate, etc .; Precious metal salts organic acids such as silver behenate, silver stcarate, etc .; Metal oxalates such as silver oxalate, nickel oxalate, etc., Met? !! carbonate such as manganese carbonate. Cobalt carbonate

;] "ff rrh! r> rif!

Iodine compounds are: zinc iodide, aluminum iodide, Aniimony iodide, ammonium iodide, indium iodide, uranyl iodide, Cadmium iodide. Potassium iodide, calcium iodide, silver iodide, cobalt iodide, zirconium iodide, mercury iodide,

s tin iodide. Strontium iodide, cesium iodide, cerium iodide, Tallium iodide. Tungsten iodide, iron iodide, copper iodide, Thorium iodide. Sodium iodide. Nickel iodide, platinum iodide, barium iodide, beryllium iodide. Magnesium iodide, Man gan iodide and lithium iodide. Also oxides of iodine like

<> Iodine pentoxide, iodine tetraoxide, etc., and iodic acid and ammonium iodate can be used. from these different iodine compounds are sulche with strong ionic coupling such as iodides of Alkali metals or alkaline earth metals are particularly preferred

Compounds that react with the iodine released from the aforementioned iodine compounds to produce an image are: starch, starch ether, amylopectin, polyvinyl alcohol. Polyvinyl formal with hr.ho

etc.; and also heterocyclic quaternary ammonium salts which can form anhydrous salts by reduction, such as 1-methyl-2.2 ', 4'-dinitrobenzyl pyridium ptolucl sulfonate, 1-methyl-4-chloroquinaldSniuni-silfate, etc .; and metal compounds such as molybdenum trioxide, thorium oxide, cerium oxide, phosphotungstic acid, phosphomolybclic acid, ammonium phosphomolybdate, etc. can be given.

As heat-sensitive color formers, individual heat sensitizers such as indo derivatives, pyrrolone derivatives and substituted aminodithin formic acid salts of heavy metals and two-component heat sensitizers such as ionic salts of long-chain aliphatic acids such as ferric stearate, phenols such as tannic acid, organic sulfonium salicylate and the like, phenols such as tannic acid, organic sulfonium salicylate, and the like, phenols such as ammonium sulfonate or chelic acid, chelic acid, or alkaline acetate Salts of organic acids with noble metals such as silver beheneate, aromatic organic reducing substances such as hydroquinone, protocatechuic acid, sulfur metal salts of higher aliphatic acids such as ferric stearate, disubstituted dithiocarbamic acid zinc derivatives such as zinc dibutyl thiocarbamate, etc. may be mentioned. In addition, there are two-component-based color-forming heat-sensitive agents such as combinations of representatives from the group of color-formable lactone compounds such as crystal violet lactone, 3-dimethyl-amino-6-methoxyfluorene; color-formable lactam compounds such as rhodamine B-lactam; Leuco compounds of dyes such as leuco crystal violet, leuco malachite green; and spiropyran compounds such as!, 3,3-trimethylindolino-8'-methoxybenzopyryl-spiran, 1-amyl-SS-dimethylindolinie-8'-ethoxybe: nzopyryl-spiran and a representative from the group of acidic compounds such as bisphenol A, "-naphthol and palmitic acid.

The incorporation of iodine compounds such as potassium iodide into a recording material was previously known, whereby a color formation occurs through iodine starch reaction through electrical excitation, whereby a visible Image can be obtained. Also, a method has been known in which iodine compounds and amines or their Leuco derivatives were incorporated into a writing layer in which iodine released by electrical means reacts with the ami ien or their derivatives, whereby an image is registered on the recording material. These known methods can also be used within the scope of the invention.

Examples of bet this procedure to be used

Zinc chloride treated cellulose, praseodymium acetate. Lanthanum propionate, nylon in question. Also can aromatic amines such as

Tetramethyl-p-phenylenediamine, Ν, Ν'-dimethyl-p-phenylenediamine,

Tetramethyldiaminodiphenylmethane, etc. can be used. In addition to these amines will be also color bases and leuco compounds such as tris (p-dimethylaminophenyl) - meihan, 3,4-Benzo-6-dimethylaminofluorene, bis (p-diethylaminophenyl) -

phenylmethoxymethane etc.
used.

There is another method of forming an image using the compounds listed below as an imaging agent, in which a writing layer containing any of these imaging elements is electrified to differentiate its properties, either hydrophilic or hydrophobic, after which it can be used as a printing form for offset printing. Pressure is used. Examples of the above-mentioned imaging element sind.Tetrazoliumsalze, Ditetrazoliumsalze, triazolium or petroleum waxes such as mikrokirstallines wax (with LSOP? ^R affine 32 to 70 carbon atoms as Hauptbestanuteil). Paraffin wax with a melting point of 37.8 to 64.5 ° C (with η-paraffin with 16 to 40 carbon atoms as the main component) and Vaseline wax with a melting point of 38 to 60 ° C.

Apart from this, it is possible that some or all of the ions A 'such as sodium ions, potassium ions, etc., which are contained in the above-mentioned porous compound A, are replaced by other ions B' such as silver ions, gold ions, copper ions, ammonium ions, Nickel ions, cobalt ions, iodine ions, iron ions, magnesium ions, etc., which are necessary for image formation, are exchanged to form a porous compound B which is used directly as the image forming agent .

The binders used here include gelatin, natural high polymers such as starch; Cellulose derivatives such as cellulose nitrate, carboxymethyl cellulose etc.; semi-synthetic polymers such as natural rubber plasticizers such. B. chlorinated rubber, cyclized Rubber, etc .; polymerization type synthetic polymers such as Polyisobutylene, polystyrene, terpene resin, polyacrylic acid,

Polvacry lai. Polymethacrylate, polyacrylonitrile,
Polyacrylamide. Polyvinyl acetate, polyvinyl alcohol,
Polyvinylpyrrolidone, polyacetal polyvinyl chloride,
Polyvinyl pyridine. Polyvinyl carbazole, polybutadiene,
Butadiene-styrene copolymers, butyl rubber,
Polyoxymethylene, Polyäthvlenimin,
Polyethyleneimine hydrochloride,

Poly (2-acryloxyethyl dimethyl sulfonium chloride) etc .;
Condensation polymers such as phenolic resin, amino resin, toluene resin, alkyd resin, unsaturated polyester resin, | ₀ allyl resin, polycarbonate, polyamide resin, polyether resin, silicone resin, furan resin, thiokol rubber, etc .; and addition polymers such as polyurethane, polyurea, epoxy resin, etc.

The recording materials according to the invention _is manufactured in the following manner:

The porous compound with contained polater substance, air-generating agent and binding agent (if necessary together with pigment, color-controlling agent and other additives) are evenly dispersed and the dispersion liquid by layer application. Dipping or other means of creating a misspelling applied to any suitable substrate. The amount of the porous compound with polar substance contained therein ranges, when using ₂ f, according to the invention in general from 30 to 38% by weight, based on the total weight of the writing layer, and preferably from 50 to 95% by weight. A particularly preferred range is from 70 to 90 wt.%, Obigeich the invention is not limited to this, ₀ special area.

Paper, resin film can be used for the substrate or the base. conductive material such as metal, with thin Metal film coated paper, vapor deposited metal coated paper, metal powder coated paper Paper, carbon treated paper, etc. can be used.

To facilitate the practice of the invention by those skilled in the art, the following are provided preferred examples are given.

example 1

Sheets of conductive recording paper were made with the following composition produced as a writing layer:

positive pole and the aluminum foil connected to the negative pole of a DC voltage source and a Voltage of approximately 150 V is applied and the pen causes the writing layer with a Speed of 1 m / s. The results obtained are shown in Table 1.

Tabel

Weight Components share Porous connection A an in Tab. 1 listed Art 100 Rutile type titanium oxide 20th Polyvinyl butyral (Degree of polymerisation 1500) 30th Ethanol 200

The above components were mixed in a ball mill for a full seven days and nights ground, after which 5 parts by weight of leuco-malachite green as an image-generating agent for this ground f> o Mixture was added and further mixed sufficiently. This mixture was then added to a Aluminum foil to a film approximately 8 ji thick applied with a squeegee. The aluminum foil coated in this way was then placed in a furnace at 10C (15 held oven ") for minutes to form a writing layer.

Then a tungsten pen with the

At connection A Descriptive hue availability Strongly acidic ion O dark green exchange resin Strongly basic ions © dark green exchange resin Montmorillonite ® green Kaolinite Δ light green Silica gel O green Silica aerosil © dark green Polyvinyl hydroquinone Δ light green Hydrophilic cinnamon O green Polymer **) Porous polyester ***) Δ light green Basic aluminum, Δ light green Magnesium carbonate **) Titanium oxide »R.-5N« χ X of the rutile type *****) Remarks:

"I from 7 parts by weight of N-vinylpyrrolidone. 3 parts by weight of methyl methacrylate and 1 part by weight of polyethylene glycol methacrylate.
*** i From I part by weight trimethyiolpropane trifumaral and

I part by weight of divinylbenzene.
***> MgAl ₂ (Om.C0 ₃ :> H ₂ 0.

**** ·> Titanium oxide, non-porous: only used for comparison purposes.

Explanation of the symbols for the »writability«:

© very good.

O gul.

Δ writable, although not good.

χ bad.

Example 2

Kaolinite, polyvinylhydroquinone, porous polyester and basic aluminum / magnesium carbonate, dk show a writability "Δ" according to Example 1 were dried under reduced pressure; thereafter, each of those listed in Table 2 below became more polar Substances adsorbed on each of these compounds A.

Then writing layers ir formed in exactly the same manner as mentioned in Example 1 and the writing layer produced in the same Way as "described" in Example 1. The following writabilities of the writing layers were measured each of the polar substances found:

Tabel

Polar substance

Glycerin

Polväthvletif> l \ kol
I. lithium chloride
Sodium chloride

Vet improvement
the description fkeil

O
Δ

continuation

Pnlure substance

Improvement University!
the describability

Monoethanolamine butyrate Δ

Sodium N-steroid sarcosinate O

Alkyltrimethylammonium Salt ®

Comment:

The symbols for improving the writability have the following meanings:

© very remarkable improvement over example 1.
○ Notable improvement over Example 1.
Δ slight improvement over example I.

From Table 2 it follows that the presence of polar Substances other than water in particular different types of electrolytes an improvement the writability serves.

Example 3

To a mixture of 2 g of ditetrazolium chloride, 10 g of polyvinyl butyral (degree of polymerization of 1500), 5 g of rutile type titanium oxide and 150 g of ethanol, 30 g of various kinds of porous compounds as shown in Table 3 below were added and the Batches kneaded or ground for two full days and nights.

The compounds of influenza A given in the table were those porous compounds which contained only the zeolitic water primarily contained in the compounds, while the compounds of group B of the table are those compounds that contain sodium chloride (NaCl) in the so-called "cavities" or "pores" that they contain.

After grinding, the liquid dispersion was applied to an aluminum-coated paper in a film thickness of about 10 μ by means of a doctor blade and then dried ^{at a temperature of 100 ° C. for 5 minutes.} After drying, the writing paper thus produced was subjected to electrical conduction recording in which a tungsten pen was connected to the negative pole and the aluminum-coated paper was connected to the positive pole of a DC voltage source and a voltage of approximately 150 V was applied and the pen was operated to move over the paper at a speed of 70 cm / s. The results of this recording are shown in Table 3 below.

Table 3

links

Writability
AWAY

Molecular sieve SK-40

Molecular sieve I3X

Molecular Sieve 5A

Weddellite

(iismondit

Chabazit

Scorodit

Clinoptilotite

Mordcnil

O
O
Δ
Δ

O O

links

Writable wedge
Λ Β

Sodalite
Analcite
Psilomelan
Concrinit

Δ
Δ
Δ
Δ

O
Δ
Δ
Δ

Meaning of the symbols for the writable wedge:

® very good.

Oh well

Δ writable, although not good.

From the foregoing it follows that the writability in the presence of the electrolyte in the porous Connection improved

Example 4

; o Using the molecular sieve SK-40 der Groups A and B of Example 3 were used to produce writing sheets and changing the writing characteristics uc5 SiiitS tested. The remedial action of the recording material or recording paper and the working conditions for the recording were exactly the same as in Example 3. The results of the tests are shown in Table 4.

Table 4

“Scanx speed Writability link of the pen link IB) (ms) IA) ® 0.7 O ® 1.0 O ® 2.0 Δ O 3.0 Δ O 4.0 Δ

The symbols given in the table have the same meaning as in example 3. From the The above experiments follow that, thanks to the presence of electrolytes, high writing speeds possible are.

Example 5

In this example, recording materials were made using a electrically conductive agent produced by adsorption of 10% aqueous Löyvngen different Electrolytes as shown in Table 5 were obtained on the porous joints.

The writing layers were then subjected to electroconductive recording and the results compare; the comparison results are given in Table 5.

Molecular sieve 13 X was impregnated with 10% strength aqueous electrolyte solution as a porous compound The type shown in Table 5 is used, with the electrolyte attached to the compound in sufficient quantity were adsorbed.

Polyvinyl butyral in a weight ratio of 5 to 1 was used as the binder. as well was used as the imaging agent triphynyl tetrazolium chloride in a weight ratio of 1/20 with respect to the total weight of the porous compound used.

Table 5

electrolyte

Sodium chloride ©

Lithium chloride ®

Sodium iodide ®

Triethanolamine cetyl sulfonate Δ Dimethylaminoacetoguanamine sulfate Δ

Potassium oleate O

Alkylbenzene calcium sulfonate O

Laurylamine hydrochloride Δ

Sodium stearyl aminopropionate O

Comment:

The symbols [Ur to improve the writability the following meaning:

® very remarkably improved writability. ^a0

O remarkably improved writability. Δ easily verbefatite writability.

E) e i s ρ i e 1 6

The scanning of the writing layer by the pen at a speed of 0.7 m / s as in Example 4 was run under the following conditions of relative humidity and writability the shift checked. The composition of the writing layer and other conditions were the same same as in Example 4; the results are given in Table 6:

24 29 10 729 18th Connection B ® Table 6 Writability © irrigation of Relative humidity Connection A © bability 1%) © O 60 © O 40 O 20th O the same 10 Δ 5 Comment: Have writable The symbols for the

interpretation as in example 4.

From the above results, it follows that there is improved writability in recordings low humidity could be achieved thanks to the presence of the electrolyte.

Example! 7th

Different types of recording materials or recording papers were used in the same way, as described in Example 1, except that different imaging agents are used instead of Leuco malachite green were used. The registration papers were described using electricity, those given in Table 7 Results were obtained.

Table 7
Image-forming agent

Leucoauramine

3.6-Di- (dimethylamino) -xanthene, 3.7-Diamino-5,10-dihydrophenazine 3,7-Di (dimethylamino) phenothiazine 4-methoxy-1-naphthol

Bis- (p-dimethy! Aminophenyl) -melhan Leukokristallvioletl

Bis (3-methyl-4-hydroxy-5-carboxyphenyl-2,6-dichlorophenylj-methane

3.6-diamino-2.7-dimethyl-9-phenylacridan 3.7-di (diethylamino) phenoxazine Indigo white

P-aminodiphenylamine

1-methyl-2.2'.4'-dinitrobenzylperidinium p-tocolsulfonate Dibromophenolsulfophthalein Phenolphthalein

Triphynyl tetrazolium chloride Di-tetrazolium chloride

Nickel oxalate

Carbonate

Silver chalk

Phosphofolfranic acid c

Nicky hypophosphile

zinc oxide

Writability Registration color polarity
of the pen O yellow + © Red + © Red + © blue © blue + O blue + © purple-blue + © purple + O rol + © blue + © dark blue + © dark blue I- © purple-blue - © Red - ü rol - © Red - © dark blue - O gray-brown - O gray-brown - O gray-brown - ® graiischwiir /. - O gray-brown - © grey black -

Example si 8

Instead of applying direct current of positive or negative polarity to the pen as in the above Example 7 was supplied with an alternating current of approximately 150 V to carry out recording in the same Imprinted in the same way as in the previous example. As a result, images or records were good without Changes in shade received.

Example 9

A mixture of the following ingredients was placed in a ball mill for two full days and nights ground to make a dispersion liquid.

component

Parts by weight

Montmorillonite
Polyvinyl butyral
(Degree of polymerisation 1500)
Sodium iodide
Ethanol

10.0

3.0

1.0

30.0

The dispersion liquid produced in this way was applied to an aluminum-coated paper in a thickness of approximately 8μ and dried to obtain the recording paper I.

On the other hand, another dispersion liquid became a mixture of the following Components are made and then applied to impregnation paper, which is dried and used for

share component Weight
share 10.0 Montmorillenite Polyvinyl alcohol Polyvinyl butyral 3.0 25 (degree of polymerization of 1000) 1.0 (Degree of polymerization of 500) 1.0 Addition (see table 9) 0.2 Sodium iodide 1.0 water 10.0 Addition (see table 8) 30.0 Ethanol

The dispersion liquid v. Produced in this way was applied to an aluminum-coated paper in a thickness of approximately 8 μ and dried to obtain a recording paper or recording material.

This recording paper was created under the same conditions as in example! with the pen to Imaging was completed, with the results shown in Table 8 being obtained.

When the above recording paper I was subjected to electroconductive registration under the same conditions as in Example 1, a light yellow portion was shown on the image recording paper. Then the papers I and II were placed on top of each other and passed through a pair of heated rollers ^{which were kept at 140 °} C. for 5 seconds, whereupon an image with a color shown in Table 9 on the image recording paper II at the light yellow portions on the recording paper I corresponded Bodies was received.

Table 8 Director color Table 9 Example 11 Registration color Zuijiz Red 60 10 g microcrystalline wax additive purple Red dark brown 45 ember rice starch purple Glutin rice starch dark brown Amylopectin dark brown Amylopectin Lanthanum propionate dark brown Lanthanum propionate dark brown Piperine blue Piperine blue Tetramethyl-paraphenylenediamine Cellulose with zinc chloride blue 50 Ν, Ν'-dimethyl-paraphenylene- blue treated blue diamine Tetramethyl paraphenylenediamine Tetramethyl-diaminodiphenyl- blue Ν, Ν'-dimethyl-paraphenylenediamine purple methane Tetramethyl-diaminodiphenylmethane Red Tris- (p-dimethylaminophenyl) - purple Tris- (p-dimethylaminophenyl) - 55 rneth'.n light yellow methane blue Without additive 3,4-benzo-6-dimethylaminofluoran very light yellow Bis (p-diethylaminophenyl) -phenyl- methoxymethane became one Without additive

Example 10

A mixture of the following ingredients was placed in a ball mill for a full two days and nights ground long to make a dispersion liquid.

Mixture of 30 g strongly basic ion exchange resin, 10 g of rutile type titanium oxide, 10 g of polyvinyl butyral (degree of polymerization of 1500) and 150 g of ethanol added and the entire batch voile for two days and nights in a ball mill to generate ground a dispersion liquid.

The dispersion liquid thus prepared was applied to an aluminum slat about 50 µm thick by means of a

Rackels in a layer thickness of about 10 ί / aufiia-Kon and dried under natural conditions / curling of a writing board. This then became a subjected to electrically conductive recording in which a Woilram pen to the negative pole and the Miiminium plate connected to the positive pole and a voltage of about 150 V has been applied, while the pen along the writing surface drove. As the current flowed, the sections became transparent and at the same time water-repellent.

The writing surface on which such an image is recorded '. • order was. was then means for offset printing an offset Abdniekvorrichuing used, with a _ ': i'cr pressure of a Hildes that could be obtained The electrically conductive image recording corresponded to the duration of use of this writing plate for olive; D'.iik uig with approximately 4,000 to 10,000 sheets.

'·. · "Steile di · ¹ - above-mentioned microcrystalline'^.!,"Sv.-'- wur <! · Paraffin wax for the I lerstclliiir_ ^T der D'ip -. 'R- ^! ops! ' . «. Sigkeii in the same way as above ■■" ■■ '. J'r.T. \ I_-rwendc The application of the dispersion · ■; -stT <ei! Au:' the writing surface, the electrically conductive ^ ■; ■ / - ^.: .'Lniii'L ".-. .: .u: ^r 'layered Sv'hreibplafe and: ■ "a -.' h !!>! gi." v.ic 'J'fsc'-Dn.ic k were in ge'Mii _ · Jer way : · · <: ■ ■■■ seeing; · jsgofuhrt. The received "·. ':': L '" i: enii: -se ·.' .ir ·. ·:! -Mk '! -,! · the bleaches as above.

ben are, for I leruellung the dispersion liquid wedge used in the same way as indicated above. That Applying the dispersion liquid to the writing plate, the electrically conductive recording on the coated shredded board and the subsequent offset printing were carried out in exactly the same way as stated above. The results obtained are shown in Table 10.

Dragonfly Kl

Hil.li.-i / i-

? .. M) iphcn \ l -'- l4 ->!> Nl-phcn \ litct ι a / oliumchl · ίίιΙ

V -ι4.4 -Hipheir. lcni-biv-

! 2. ^;; -diphen> lletraziiliiiinchlonil]

.-.> · Ι> ι.ιιιΐΜ> Ι-Ιιΐν-

I 4.4 -i.VNiliphiMn ll-tetr.i / iiliunicli

C Il

■ - '. · Mixture d' .- r

■ "/ ·.". I; · um ener

i ->! ge ". the · Bo-iandieiie became; n le / '* c ^: T.itre and Nachte lang / nr ersiortfinsmkv. ·!' ground.

VPr-er. '. I-2.J-hi' .- (p-dipr.ep '.!) -; e "" azo! Iu; iK hiond
■ .: .. asr.artiger s ¹ . ntheüsche:
/ ■ - .. 'VfMf.iekLiicirsieh ■ 3 X)
> -.:-ov.:dw,rr. Ρ. Ϋ ν. ρ

Mentre

6 g N \

500)

10 g! 50 i?

The resulting dispersion liquid was reduced to a minimum range of about 50%. Thickness using s;. "Ei to ^Rackeis;; -ier Fiimdicke 'ur.cl applied .on about 10 ^//;, r / er ge-Tockr.et natural conditions Thereafter, the writing surface of a conductive ■ siektrisch recording has been subjected. in that ϊ \ - Woiirarr. pen with the negative pole and the A: u ~: - :: un ", pla '.". e with the positive Po! an S'.rom- :.' ■ '. € λ ve-bun rl · -; - -ind a current of about! 50V - • .jfeepragi w-jrde. while the pen moved along the writing plate with a »scanning speed of 50 cm / s. As a result of the electrical current flow, took the stressed part took on a reddish-purple color and at the same time became water-repellent.

The writing plate with the image thus recorded was then offset printed with an offset printing apparatus subjected to a good print of an image corresponding to the electrical image recording could be obtained. The service life of this described plate for offset printing was included approximately 3000 to 5000 prints.

Instead of the above-mentioned 5-phenyl-23-bis (p-diphen \ i) -tetrazolium chloride different imaging agents were used, as shown in Table! 0 - (C Hi.

NO ₂

2.2'.5.5'-Teira-p-nitropheny! -3.3'-13.3 '-dimethox y-4.4'-biphenj len) -diteira7oiiumchlorid

3.3-Dimethoxv-4.4'-diphenylene-3.3 "-bisf 2-phenyl-5- (2-hydroxy phenyl i-tetrazoliurressigiäuresalz]

2.5-Diphenyl-3- (4-nitrophenyl) -tetrazolium fluoroborate

Comment :
© very jui

Example I 3

Molecular sieve 13Λ, strongly acidic ion exchange resin and betonil (Toriiiuncral der Mo.itmorillonitgruppe) were selected as porous compound A and each of these substances underwent an exchange reaction in an aqueous solution to a sufficient degree with each of the different cations ß 'that contribute to the image formation, e.g. . B. silver ions, copper ions, nickel ions, cobalt ions and zinc ions, to produce different compounds B are subjected.

After the compounds B had been dried in vacuo, 50 g of each were added to a mixture of 15 g of polyvinyl butyral (degree of copolymerization of 1500), 10 g of titanium oxide and 100 g of ethanol, and the entire batch in a ball mill for a full two days

and milled overnight to make a dispersion liquid wedge.

The dispersion liquid thus obtained was then applied to an electrically conductive carbon paper with a knife in a coating thickness of 10 μm and ^{dried for 2 minutes at a temperature of 100 °} C., whereby conductive recording paper or recording material was obtained.

Thereafter, the recording paper was subjected to electrically conductive recording by using a tungsten pen with the negative pole and the conductive carbon paper with the positive pole Power source was connected and a direct current of about 200 V was applied while the writing elevator was on the Tracing paper moved along at a speed of 50 cm / s. The results are in Table 11 reproduced.

Table I I. Porous Describe I arhton Austai- Ver hindunii bar wedge KaIi (Wed B Molecular ® greyish silver sieve ΠΧ black / the same ® Brown copper the same ® Brown nickel the same O Brown cobalt the same O Brown zinc strongly acidic O greyish silver ionic black exchange resin the same O Brown copper the same O Brown nickel the same O Brown cobalt the same Δ Brown zinc Bentonite O Brown silver the same Δ Brown copper the same Δ Brown nickel the same Δ Brown cobalt the same Δ Brown zinc Comment: Hie Svmhoie mean for the description harkcil: ® * Ehr gui
O! IUt. ~ ι Δ acceptable.

Example 14

In the dispersion liquid of Example 13, 2 g of each of those shown in Table 12 was added uniformly dispersed electrolytic color former and the image recording is carried out in the same way

Tatille 12

leads as in Example 1. As a result , two color images were obtained by reversing the polarity of the pen from positive to negative and vice versa. Al: porous compound B was used molecular sieve 13 .Y exchanged with silver ions. The results are shown in Table 12.

Electrolytic color former

Registration color Registration color

(with positive (with negative

Polarity of the pin) polarity of the pin)

Leucoauramine yellow

3,6-di (dimethylamino) xanthene red

3,7-diamino-5-phenyl-5, 10-dihydrophenazine red

Leuco malachite green green

4-methoxy-l-naphthol blue

greyish black greyish black greyish black greyish black greyish black

For this 1 sheet of drawings 809 634/31!

Claims (6)

Patent claims: 1. Image recording material for electrical registration or image recording with a containing at least one electrically conductive compound, an imaging agent and a binder Recording layer on a carrier, characterized in that it has at least one electrically conductive connection porous compound with polar substance contained in it - with the exception of zeolitic ones Compounds containing water - contains 2. Recording material according to claim 1, characterized in that the registering or Writing layer is a single layer that contains at least one representative from the group of porous Compounds with polar substance contained therein and an image-forming agent 3. Recording material according to claim 1, characterized in that the registering or Writing layer comprises a conductive layer which has at least one member from the group of contains porous compounds with polar substance contained therein and an image-forming layer, J.s which contains at least one image-forming agent, wherein the image-forming layer on the conductive Layer is piled up. 4. Recording material according to claim 1, characterized in that the one polar 3c Substance-containing porous compound at least one representative from the group of ion exchange resins, Electron exchange resins, hydrophilic crosslinked polymers, porous polyester resins and microporous body of copolycondensed resins of dichlorodiphenylsulfr -: and bisphenol is, each of which has at least one representative from the group of polar solvents, inorganic Contain electrolytes and organic electrolytes. 5. Recording material according to claim 1, characterized in that one is polar Substance-absorbing or containing porous compound at least one representative from the group which is silicas, silicates, aluminum silicates and basic aluminum / magnesium carbonates in each case at least one representative from the group of polar solvents, inorganic electrolytes and organic electrolytes. 6. Recording material according to claim 1, characterized in that the proportion of the polar substance-containing porous compounds in the recording or writing layer from 30 to 98% by weight and in particular 70 to 90% by weight, based on the total weight of the writing layer, enough.